The new compounds LaSrSiO3N and LaBaSiO3N activated with Eu2+ are orange-red light-emitting luminescent materials under excitation in the UV-blue range. They represent the first examples of stoichiometric alkaline earth oxynitridosilicates with a β-K2SO4 structure. The isostructural compound LaEuSiO3N is ferromagnetic with a Curie temperature of 3 K and also shows red luminescence (λmax = 705 nm) under excitation at 405 nm.